CATALYTIC FUJIWARA-MORITANI REACTION. CHALLENGES IN C-H ACTIVATION AND CATALYST OXIDATION. Laura...
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CATALYTIC FUJIWARA-MORITANI REACTION. CHALLENGES IN C-H
ACTIVATION AND CATALYST OXIDATION.
Laura Ruiz Espelt
Yoon Group
University of Wisconsin-Madison
Literature Seminar
April 7, 2011
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• Discovered in 1968 independently by Mizoroki and Heck
• Attractive transformation for C-C bond formation
• Richard F. Heck obtained the Nobel Prize on 2010
• Intensively developed from synthetic and mechanistic point of view
Oestrich, M. The Mizoroki-Heck Reaction; John Wiley & Sons, 2009
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Garg, N.K.; Caspi, D.D.; Stoltz, B.M. Synlett 2006, 18, 3081
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Garg, N.K.; Caspi, D.D.; Stoltz, B.M. Synlett 2006, 18, 3081
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Garg, N.K.; Caspi, D.D.; Stoltz, B.M. Synlett 2006, 18, 3081
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Moritani, I.; Fujiwara, Y. Tetrahedron Lett. 1967, 12, 1119
Fujiwara, Y.; Moritani, I.; Matsuda, M.; Teranishi, S. Tetrahedron Lett. 1968, 5, 633
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Fujiwara, Y.;Asano, R.; Moritani, I.; Teranishi, S. J. Org. Chem. 1976, 41, 1681
Fujiwara, Y.;Asano, R.; Moritani, I.; Teranishi, S.J. Org. Chem. 1976, 41, 1681
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Fujiwara, Y.; Moritani, I.; Danno, S.; Asano, R.; Teranishi, S. J. Am. Chem. Soc. 1969, 7166
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Fujiwara, Y.; Moritani, I.; Danno, S.; Asano, R.; Teranishi, S.J. Am. Chem. Soc. 1969, 7166
Oestrich, M. The Mizoroki-Heck Reaction; John Wiley & Sons, 2009, p. 14
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Challenge 1: C-H Activation
Challenge 2: Pd(0) Oxidation
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1. C-H bonds easier to activate2. Complete ortho regioselectivity for symmetrical substrates
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Cai, G.; Fu, Y.; Li, Y.; Wan, X.; Shi, Z. J. Am. Chem. Soc. 2007, 129, 7666
Shi (2007)
Satoh and Miura (2009)
Umeda N.; Hirano, K.; Satoh, T.; Miura, M. J. Org. Chem. 2009, 74, 7094
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- Entry into phthalide core
- Reaction catalyzed by [Pd] cyclizes after first vinylation
- Reaction catalyzed by [Rh] suffers a second vinylation before the cyclization step
- No mechanistic insightUeura, K.; Satho, T.; Miura, M. Org. Lett. 2007, 9, 1407-1409
Miura, M.; Tsuda, T.; Satoh, T.; Pivsa-Art, S.; Nomura, M. J. Org. Chem. 1998, 63, 5211-5215
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Ryabov, A.D.; Sakodinskaya, I.K.; Yatsimirsky, A.K. J. Chem. Soc. Dalton Trans. 1985, 2629
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Davies, D.; Donald, S.M.A.; Macgregor, S.T. J. Am. Chem. Soc. 2005, 127, 13754
BP86 / 6-31G**
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- Short distance between Pd and H
- Elongated C-H bond
- No charge change in aromatic ring
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Maehara, A.; Tsurugi, H.; Satoh, T.; Miura, M. Org. Lett. 2008, 10, 1159
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Ferreira, E.; Stoltz, B.M. J. Am. Chem. Soc. 2003, 125, 9578
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Zhang, Y.; Shi, B.; Yu, J.Q. J. Am. Chem. Soc. 2009, 131, 5072
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0.05 Ålonger than
Pd(Pyr)2(OAc)2
- Origin of meta selectivity still unclear
Zhang, Y.; Shi, B.; Yu, J.Q. J. Am. Chem. Soc. 2009, 131, 5072
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Wang, D.; Engle, K.; Shi, B.; Yu, J.Q. Science. 2010, 327, 315
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Engle, K.M.; Wang, D.; Yu, J.Q. J. Am. Chem. Soc. 2010, 132, 14137
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Engle, K.M.; Wang, D.; Yu, J.Q. J. Am. Chem. Soc. 2010, 132, 14137
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Engle, K.M.; Wang, D.; Yu, J.Q. J. Am. Chem. Soc. 2010, 132, 14137
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Many improvements achieved since Fujiwara’s initial observations
Two main tactics used to achieve regioselectivity:
1. Directing groups- site selective palladation
2. Ligands- not fully understood
More “synthetically appealing” directing groups design: traceless directing groups
Future of ligands to direct reactivity and selectivity
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Fujiwara (1968)
Itahara (1983)
Fujiwara, Y.; Moritani, I.; Matsuda, M.; Teranishi, S. Tetrahedron Lett. 1968, 35, 3863
Itahara, T.; Ikeda, M.; Sakakibara, T. J. Chem. Soc. Perkin Trans 1. 1983, 1361
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“Green Oxidants”: O2
Pros: - Environmentally friendly - Lower cost - Increase in atom efficiency - Facilitate product isolation
Stahl, S. Angew. Chem. Int. Ed. 2004, 43, 3400
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Cons: - O2 requires rigorous safety handling - Slow electron transfer compared to decomposition of the reduced metal
“Green Oxidants”: O2
Solution: - Use of ligands to stabilize Pd0 so that is stable under oxidative conditions
- Use an electron-transfer mediator to carry the electrons from Pd0 to terminal “green oxidant’
Piera, J.; Backvall, J.E. Angew. Chem. Int. Ed. 2008, 47, 350610
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Yokota, T.; Tani, M.; Sakaguchi, S. Ishii, Y. J. Am. Chem. Soc. 2003, 125, 1476
Want, J.; Yang, C.; Liu, L.; Guo, Q. Tet. Letters. 2007, 48, 5449
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Shue, R.S. Chem. Commun. 1971, 1510
Dams, M.; De Vos, D.E.; Celen, S.; Jacobs, P.A. Angew. Chem. Int. Ed. 2003, 42, 3512
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Ferreira, E.; Stoltz, B.M. J. Am. Chem. Soc. 2003, 125, 9578
Engle, K.M.; Wang, D.; Yu, J.Q. J. Am. Chem. Soc. 2010, 132, 14137
2 equiv
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Challenge: Use a Directing Group that acts also as the Oxidant:
OXIDIZING DIRECTING GROUPS
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Rakshit, S.; Grohmann, C.; Besset, T.; Glorius, F. J. Am. Chem. Soc. 2011, 133, 2350
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Wu,J.; Cui, X.; Chen, L.; Jiang, G.; Wu, Y. J. Am. Chem. Soc. 2009, 131, 13888
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Rakshit, S.; Grohmann, C.; Besset, T.; Glorius, F. J. Am. Chem. Soc. 2011, 133, 2350
Wu,J.; Cui, X.; Chen, L.; Jiang, G.; Wu, Y. J. Am. Chem. Soc. 2009, 131, 13888
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Pauterau, F.W.; Besset, T.; Glorius, F.Angew. Chem. Int. Ed. 2011, 50, 1064
Cho, S.H.; Hwang, S.J.; Chang, S.J. Am. Chem. Soc. 2008, 130, 9254
Wu,J.; Cui, X.; Chen, L.; Jiang, G.; Wu, Y.J. Am. Chem. Soc. 2009, 131, 13888
Rakshit, S.; Grohmann, C.; Besset, T.; Glorius, F. . Am. Chem. Soc. 2011, 133, 2350-2353
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Two main tactics used to achieve regioselectivity:
1.Directing groups 2. Ligands
Oxidation on catalyst achieved by:
1. Stoichiometric oxidants such as Cu(OAc)2
or AgOAc
2. Oxygen in the presence of electron-
transfer-mediators such as Cu(OAc)2 or
polyoxometallate acids
3. Oxygen as sole oxidant in the presence
of ligands to stabilize the metal
Oxidizing directing group opens new avenues for this chemistry Advantages/ disadvantages have to be evaluated individually
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Thank you!
The Yoon Group
Practice Talk Attendees:
Travis Blum Shishi LinJamie Chen Zic LuMegan Cismesia Jon ParrishJuana Du Derek SalterOlga Dykhno Liz TysonElliot Farney Kevin WilliamsonAnna Hurtley Adam Weinstein
Professor Tehshik Yoon
Kat Myhre